Heteroatom-functionalized porphyrazines and multimetallic complexes and polymers derived therefrom

Abstract

Porphyrazine compounds having moieties substituted at the eight peripheral .beta.-pyrrole positions are disclosed. The porphyrazine compounds have the general structural formula: ##STR1## wherein M is H.sub.2 or a metal capable of complexing with the pyrrole nitrogen atoms, and A, B, C and D are independently selected from the group consisting of a thio moiety, an amino moiety, an oxo moiety, a phospho moiety, a seleno moiety, a telluro moiety and a non-coordinating moiety, like a hydrocarbon moiety, with the proviso that not all of A, B, C and D are a thio moiety and that not all of A, B, C, and D are a hydrocarbon moiety. The porphyrazine compounds, depending on the identity of A, B, C and D, are capable of complexing one to four metal ions to the periphery of the porphyrazine to form a multimetallic porphyrazine. Multimetallic porphyrazine compounds can be linked by the peripherally-complexed metal ions to form a linear, i.e., ribbon, polymer or a two-dimension, i.e., sheet polymer. The porphyrazine compounds, and the multimetallic complexes and polymers derived therefrom, are useful in, or as, magnet materials, molecular metal conductors, pharmaceuticals, imaging agents, and dyes.

Claims

1. A heteroatom-functionalized porphyrazine compound having the structure: ##STR49## wherein M is 2H or an element capable of complexing with pyrrole nitrogen atoms, and A, B, C and D are independently selected from the group consisting of:

(a) a thio moiety, said thio moiety selected from the group consisting of sulfo; sulfhydryl; alkylthio (--SR), wherein R is an alkyl group having one to 10 carbon atoms, a polyethylene oxide chain having one to twenty ethylene oxide units, phenyl, benzyl or allyl, or R is a benzyl blocking group; --SSi(R.sub.7).sub.3, wherein the R.sub.7 groups are independently selected from an alkyl group having one to 16 carbon atoms and phenyl; --SCH.sub.2 (CH.sub.2).sub.c O(CH.sub.2 (CH.sub.2).sub.c O).sub.d R.sub.9 or --SCH.sub.2 (CH.sub.2).sub.c S(CH.sub.2 (CH.sub.2).sub.c O).sub.d R.sub.9, wherein c is one or two, d is an integer from one to five, and R.sub.9 is hydrogen or an alkyl group having one to 16 carbon atoms; --SCH.sub.2 (CH.sub.2).sub.c E(CH.sub.2 (CH.sub.2).sub.c F).sub.d R.sub.9, wherein E and F are independently selected from the group consisting of selenium, tellurium, alkylamino wherein the alkyl group has one to 16 carbon atoms, alkyl wherein the alkyl group has two to ten carbon atoms, p-toluenesulfonamide, 2-pyridylmethyl, COCH.sub.2 COR.sub.9, CH.sub.2 COCH.sub.2 COR.sub.9, CH.sub.2 CO.sub.2 H, and acetamide; trithiocarbonate; and --S--(CH.sub.2 --S).sub.q --, --S--(CH.sub.2 CH.sub.2 --S).sub.q --, or --S--(CH.sub.2 CH.sub.2 CH.sub.2 --S).sub.q --, wherein q is an integer from 2 through 6;

(b) an amino moiety, said amino moiety selected from the group consisting of ##STR50## wherein R.sub.1 and R.sub.2 are independently selected from the group consisting of hydrogen, an alkyl group having one to 16 carbon atoms, 2-pyridylmethyl, benzyl, allyl, --CH.sub.2 CO.sub.2 H, --COCH.sub.2 OR.sub.15, and --CH.sub.2 OCCH.sub.2 COR.sub.15, wherein R.sub.15 is an alkyl group having one to 16 carbon atoms; --NR.sub.16 --(CH.sub.2).sub.q --NR.sub.16 --; --NR.sub.16 --(CH.sub.2 CH.sub.2 CH.sub.2 NR.sub.16).sub.q --CH.sub.2 CH.sub.2 CH.sub.2 NR.sub.16 --; --NR.sub.16 --(CH.sub.2 NR.sub.16).sub.q --CH.sub.2 NR.sub.16 --; and --NR.sub.16 --(CH.sub.2 CH.sub.2 --NR.sub.16).sub.q CH.sub.2 CH.sub.2 NR.sub.16 --, wherein q is an integer from 2 through 6, and R.sub.16 is hydrogen, an alkyl group having one to ten carbon atoms, 2-pyridylmethyl, benzyl, allyl, --CH.sub.2 CO.sub.2 H, --COCH.sub.2 OR.sub.10, or --CH.sub.2 OCCH.sub.2 COR.sub.10, wherein R.sub.10 is an alkyl group having one to 12 carbon atoms;

(c) an oxo moiety, wherein said oxo moiety is selected from the group consisting of:

hydroxyl; alkoxy (--OR.sub.17); acyloxy (--OCOR.sub.17); silyloxy (--OSi(R.sub.17).sub.3), wherein R.sub.17 is an alkyl group having one to 12 carbon atoms, benzyl or phenyl; a ring containing at least two oxygen atoms; a ring containing at least one oxygen atom and either one nitrogen, sulfur, phosphorus, tellurium or selenium atom; carbonate; --O--((CH.sub.2).sub.t --X).sub.v --O--, wherein X is sulfur, oxygen, phosphorus, selenium, tellurium, or --NR.sub.11, wherein R.sub.11 is selected from the group consisting of hydrogen, an alkyl group having one to six carbon atoms, 2-pyridylmethyl, benzyl, allyl, --CH.sub.2 CO.sub.2 H, --COCH.sub.2 OR.sub.10, and --CH.sub.2 OCCH.sub.2 COR.sub.10, wherein R.sub.10 is an alkyl group having one to twelve carbon atoms, v is an integer 1 through 6, and t is an integer 1 through 3; and a ring having the structure ##STR51## wherein q is an integer from 2 through 6, and wherein the oxygen atoms can be substituted, individually or collectively, with nitrogen, sulfur, phosphorus, tellurium or selenium;

(d) a phospho moiety, wherein the phospho moiety is selected from the group consisting of alkylphosphino (--PR.sub.3 R.sub.4), wherein R.sub.3 and R.sub.4 can be the same or different and are alkyl groups having one to 12 carbon atoms, benzyl, phenyl, polyethyleneoxy or polyphenyl ether; a phosphonate ester (P(OR.sub.5)).sub.2, wherein R.sub.5 is an alkyl group having 1 to 12 carbon atoms or phenyl; ##STR52## wherein R.sub.5 is hydrogen, an alkyl group having 1 to 3 carbon atoms or phenyl;

(e) a seleno moiety;

(f) a telluro moiety, wherein the seleno moiety or telluro moiety is selected from the group consisting of seleno (--SeH or --Se.sup.-); telluro (--TeH or Te.sup.-); alkylseleno; alkyltelluro (--Se(Te)R.sub.6), wherein R.sub.6 is an alkyl group having one to 12 carbon atoms, allyl, phenyl or benzyl; --Se(Te)M.sup.2, wherein M.sup.2 is an alkali metal ion or an alkaline earth metal ion; --Se(Te)Si(R.sub.7).sub.3, wherein the R.sub.7 groups are independently selected from an alkyl group having one to 12 carbon atoms and phenyl; --Se(Te)CH.sub.2 C.sub.6 H.sub.4 --4--CO.sub.2 R.sub.8, R.sub.8 is an alkyl group having one to six carbon atoms or phenyl; --Se(Te)CH.sub.2 (CH.sub.2).sub.c O(CH.sub.2 (CH.sub.2).sub.c O).sub.d R.sub.9; --Se(Te)CH.sub.2 (CH.sub.2).sub.c S(CH.sub.2 (CH.sub.2).sub.c O).sub.d R.sub.9, wherein c is one or two, d is an integer from one to five, and R.sub.9 is hydrogen or an alkyl group having one to 12 carbon atoms; and --Se(Te)CH.sub.2 --(CH.sub.2).sub.c E(CH.sub.2 (CH.sub.2).sub.c F).sub.d R.sub.9, wherein E and F are independently selected from the group consisting of selenium, tellurium, alkylamino (wherein the alkyl group has one to five carbon atoms), alkyl (wherein the alkyl group has two to ten carbon atoms), 2-pyridylmethyl, --COCH.sub.2 COR.sub.9, --CH.sub.2 COCH.sub.2 COR.sub.9, p-toluenesulfonamide and acetamide;

and (g) a hydrocarbon moiety, wherein the hydrocarbon moiety is selected from the group consisting of hydrogen; an alkyl group having one to 18 carbon atoms; phenyl; alkyl phenyl; alkoxyphenyl, wherein the alkyl or alkoxy group has one to 12 carbon atoms; benzo; and polyethyleneoxyphenyl;

with the proviso that not all of A, B, C and D are thio moieties and that not all of A, B, C and D are hydrocarbon moieties, and wherein one or more of A, B, C and D is capable of complexing with a metal ion M.sup.1.

2. The compound of claim 1 wherein at least two of A, B, C and D are capable of complexing with the metal ion M.sup.1.

3. The compound of claim 1 wherein at least three of A, B, C and D are capable of complexing with the metal ion M.sup.1.

4. The compound of claim 1 wherein A, B, C and D each are capable of complexing with the metal ion M.sup.1.

5. The compound of claim 1 wherein A and B are capable of coordinating with the metal ion M.sup.1.

6. The compound of claim 1 wherein A and C are capable of coordinating with the metal ion M.sup.1.

7. The compound of claim 1 wherein M is selected from the group consisting of two hydrogen atoms, an alkali metal, an alkaline earth metal, a transition metal, a lanthanide, an actinide, aluminum, gallium, indium, thallium, germanium, tin and lead.

8. The compound of claim 1 wherein M is selected from the group consisting of nickel, copper, two hydrogen atoms, magnesium, iron, aluminum, manganese, gadolinium, rhodium, a lanthanide, an actinide, gold, cobalt, platinum, palladium, ruthenium, lead, lithium, zinc, chromium, technetium, silicon, indium, thallium, germanium, tin, tungsten, rhenium, zirconium, iridium, uranium, vanadium, titanium, molybdenum, gallium, neodymium, and ytterbium.

9. The compound of claim 1 wherein the two A moieties, the two B moieties, the two C moieties or the two D moieties can be taken together to form a ring.

10. The compound of claim 1 wherein M.sup.1 is selected from the group consisting of a transition metal, a lanthanide, an actinide, an alkali metal, an alkaline earth metal, aluminum, gallium, indium, thallium, germanium, tin and lead.

11. The compound of claim 1 wherein M.sup.1 is selected from the group consisting of Pt, Sn, Ni, Hg, Ga, Mn, Cu, Cr, Fe, Gd, Si, Zn, Mo, Ru, Rh, Mg, Ti, V, Pd, Cd, Au, Tc, Eu, Sm, Ce, and Th.

12. The compound of claim 1 having the structure: ##STR53## wherein n is 1 or 2.

13. The compound of claim 1 having the structure: ##STR54## wherein R.sub.1 and R.sub.2 are independently selected from the group consisting of hydrogen, an alkyl group having one to 16 carbon atoms, 2-pyridylmethyl, benzyl, allyl, --CH.sub.2 CO.sub.2 H, --COCH.sub.2 CR.sub.15 and --CH.sub.2 COCH.sub.2 COR.sub.15, wherein R.sub.15 is an alkyl group having one to 16 carbon atoms.

14. The compound of claim 1 having the structure: ##STR55##

15. The compound of claim 1 having the structure: ##STR56## wherein R.sub.12 is an alkyl group having one to 10 carbon atoms or --CO.sub.2 H.

16. The compound of claim 1 having the structure: ##STR57## wherein Bnbe is p-carboxybutyl benzyl.

17. The compound of claim 1 having the structure: ##STR58## wherein Pyr is 2-pyridylmethyl and n is 1 or 2.

18. The compound of claim 1 having the structure: ##STR59## wherein Me is methyl.

19. The compound of claim 1 having the structure: ##STR60## wherein R.sub.14 is an alkyl group having one to 10 carbon atoms.

20. The compound of claim 1 having the structure: ##STR61## wherein w is an integer 0 through 3, R.sub.13, independently, is hydrogen, an alkyl group or an alkoxy group having one to ten carbon atoms, polyethyleneoxy or polyphenoxy.

21. A multimetallic porphyrazine compound comprising a heteroatom-functionalized porphyrazine compound of claim 1 and one or more M.sup.1 metal ions complexed to the periphery of the heteroatom-functionalized porphyrazine compound.

22. The multimetallic compound of claim 21 having the structure: ##STR62## wherein L is a ligand to complete the coordination shell of M.sup.1, and p is an integer from 0 through 10.

23. The multimetallic compound of claim 21 having the structure: ##STR63## wherein L is a ligand to complete the coordination shell of M.sup.1, and p is an integer from 0 through 10.

24. The multimetallic compound of claim 21 having the structure: ##STR64## wherein L is a ligand to complete the coordination shell of M.sup.1, and p is an integer from 0 through 10.

25. The multimetallic compound of claim 21 having the structure: ##STR65## wherein L is a ligand to complete the coordination shell M.sup.1, and p is an integer from 0 through 10.

26. The multimetallic compound of claim 21 having the structure: ##STR66## wherein L is a ligand to complete the coordination shell of M.sup.1, and p is an integer from 0 through 10.

27. The multimetallic compound of claim 21 having the structure: ##STR67## wherein L is a ligand to complete the coordination shell of M.sup.1.

28. The multimetallic compound of claim 21 having the structure: ##STR68## wherein Et is ethyl.

29. The multimetallic compound of claim 21 having the structure: ##STR69##

30. The multimetallic compound of claim 21 having the structure: ##STR70## wherein M is Ni(II), Cu(II) or Mn(II), bipy is bipyridyl, terpy is terpyridyl and Me is methyl.

31. The compound of claim 1 having the structure: ##STR71## wherein w is an integer 0 through 3, R.sub.13, independently, is selected from the group consisting of hydrogen, an alkyl group or an alkoxy group having one to ten carbon atoms, phenyl, alkylphenyl or alkoxyphenyl wherein the alkyl or alkoxy group has 1 to 12 carbon atoms, polyethyleneoxy and polyphenoxy.